Pourable and free-flowing detergent, wetting, and emulsifying compositions



NOV. 7, 1967 w, STElN ET AL 3,351,559

Y POURABLE AND FREE-FLOWING DETERGENT, WETTING, AND

EMULSIFYING COMPOSITIONS Filed Oct. 8, 1964 United States Patent Office 3,351,559 Fatented Nov. 7, 1967 3,351,559 POURABLE AND FREE-FLOWING DETER- GENT, WETTING, AND EMULSIFYING CGMPOSlTlONS Werner Stein, Erlrrath-Unterbach, Herbert Weiss, Cologne Dentz, and Otto Koch, Hilden, Rhineland, Germany, assignors to Henkel & (lie, G.m.h.H., Dusseldorf, Germany, a corporation of Germany Filed Oct. 8, 1964, Ser. No. 402,627 Claims priority, application Germany, Nov. 13, 1963, H 50,823 (Ilaims. (Cl. 252--138) This invention relates to new and improved detergent preparations which have excellent detergent, wetting, and emulsifying properties, and more particularly this invention relates to detergent, wetting, and emulsifying agents which are characterized by their ability to flow freely and the absence of any tendency on their part to cake even when stored for prolonged periods.

The non-ionic surface-active agents are produced, in their technical manufacture, in the form of oily or pastelike, or even semisolid masses, and, in contrast to other surface-active agents, such as the anionic, they cannot be converted into powders having a high surface-active agent content. Numerous attempts have been made to produce pourable detergents having a satisfactory content of non-ionic surface-active material. For example, it has been proposed to mix the non-ionic surface-active agent with inorganic salts which are manufactured by calcination. According to another proposal, anhydrous phosphates having an especially low bulk weight have been suggested as suitable for binding non-ionic surfaceactive agents.

It is an object of the invention to improve the pouring and shelf-like properties of free-flowing detergent, wetting, and emulsifying compositions. A still further object of the invention is to provide effective detergent, Wetting, and emulsifying agents in a solid form characterized by improved pouring, shelflife, and stability properties.

Still a further object of the invention is to provide highly effective detergent, wetting, and emulsifying compositions containing as active ingredients non-ionic surface-active agents.

A still further obejct of the invention is to provide highly active detergent, wetting, and emulsifying compositions containing as active ingredients non-ionic surface-active agents, as well as commercially attractive methods for preparing the same.

Further objects and advantages will become apparent in the course of the following description.

In accordance with the invention it has now been found that the above difficulties in pourability and storage may be overcome and detergents, wetting agents, and emulsifiers of improved efliciency in various forms, such 'as for example flakes, powders, etc., containing as active ingredient, non-ionic surface-active agents, may be obtained by adding to or incorporating therewith an amount of a sulfo-fatty acid salt having 8 to 2.4 and preferably 10 to 18 carbon atoms in their molecules. The advantage of the invention can readily be appreciated from the fact that the substances, i.e., sulfo-fatty acid salts used for improving the powder properties of the detergent themselves possess surface activity and therefore do not constitute ballast materials in the final preparation.

Pourable or free-flowing preparations are defined as those whose particle size is so small that they are usually poured when they are being packed or when they are being used by the consumer. They include, for example, the various types of powders, such as hollow bead powders, which are obtained by the conventional methods for the. production of powdered detergents as Well as granulates, agglomerates, etc. Other forms of pourable and free-flowing preparations are also within the scope of the invention including such examples as needles, ribbons, flakes, etc., as prepared with extrusion machines.

The non-ionic surface-active agents to be used in the compositions in accordance with the invention consist of compounds having hydrophobic radicals containing at least 8 and preferably 10 to 24 and most preferably 12 to 18 carbon atoms, which radicals are linked directly or through intermediate groups with non-ionic solubilizing radicals. The hydrophobic radicals are straight chain or branch chain alkyl radicals and may be derived from the fatty acid or fatty alcohol radicals or from an alkylaryl compound. Aggregations of hydroxyl groups, ethylene glycol radicals, or amino oxide radicals are satisfactory as non-ionic solubilizing groups. The hydrophobic radicals and non-ionic solubilizing groups can be linked together by ether or thioether atoms, aminonitrogen atoms, ester groups, carboxylic or sulfonic acid amide groups, etc.

The non-ionic surfactants which have proved most advantageous are the etherification products of hydro phobic organic hydroxyl group containing compounds with a polyethylene glycol or the esterification products of a hydrophobic acid, preferably a carboxylic acid with a polyethylene glycol. Generally, these compounds are prepared by addition of ethylene oxide to a hydrophobic starting material containing an active hydrogen atom; the number of ethylene glycol radicals present in the molecule must be sufficient for the resulting compound to be water-soluble. The amount of ethylene glycol radicals required for this water solubility varies with the chain length of the hydrophobic radicals. Frequently, 4 to 16 ethylene glycol radicals per molecule produce sulficient water solubility. The number of ethylene glycol radicals can, however, amount to 20, 30, 40, 60 Or up to per molecule.

Examples of non-ionic surfactants suitable for use in accordance with the invention include the addition products of ethylene oxide with fatty alcohols, alkylphenols, fatty acids, fatty acid amides, fatty acid alkylol amides, alkyl sulfonic acid amides, alkyl benzene sulfonic acid amides, alkyl-benzene sulfonic acid alkylol amides, partial ethers of fatty alcohols, partial esters of fatty acids of polyvalent alcohols, etc. The latter compounds also include partial ethers or partial esters de rived from glycerin or from polyglycerins, such as those obtained, for example, by condensing a glycide with a fatty alcohol or fatty acid.

If the partial ethers or partial esters contain at least 3 and preferably 4- to 10 free hydroxyl groups in the molecule, they often have sufficient water solubility for satisfactory use in accordance with the invention even without the further addition of ethylene oxide.

The compounds which can be used according to the invention, however, also include those in which hydrophobic organic compounds containing an active hydrogen atom are first reacted with a higher alkylene oxide, such as propylene or butylene oxide, and thereafter ethylene oxide is added on until water solubility is achieved. It is also possible to prepare water-soluble materials by the addition of sufficient ethylene oxide, followed by addition of limited amounts of propylene oxide, that is, additions in sufliciently small amounts that the final compounds remain water'soluble. These non-ionic surfaceactive agents are characterized by their especially low suds-producing properties.

Further, non-ionic substances which are suitable for use according to the invention include those non-ionic products known under the trade names Pluronics or Tetronics. Pluronics are those polyethers having polypropylene glycol chains which are water-insoluble in themselves, but which are linked with solubilizing ethylene glycol chains and thereby made water-soluble. The Tetronics designate a variant of these compounds in which several propylene glycol chains are linked with the nitrogen atoms of a central amine radical, preferably an alkylene diamine radical, terminating in water-solubilizing propylene glycol chains.

The surface active aminooxides which can be used according to the invention include those products in which the hydrophobic radical and the radical bearing the aminooxide group are separated from one another by ether or thio-ether groups. The ether groups are present peferably in the form of ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycide or polyglycerin radicals. Such amino-oxides are obtainable by the methods described in United States application Ser. No. 118,258, filed June 20, 1961.

Many surface-active amino-oxides and a number of surface-active fatty acid esters or fatty alcohol ethers of water-soluble carbohydrates, especially sugars, are readily differentiated from other oily to pasty surface-active preparations by their satisfactory powder properties. Nevertheless, the pulverulence properties of the pourable freeflowing products made therefrom can be improved by the use of sulfo-fatty acid salts.

The sulfo-fatty acids suitable for use according to the invention or their salts are derived from saturated straight-chained or branched fatty acids having to 24, and preferably 12 to 18 carbon atoms. The sulfonic acid group preferably being in the OL-POSI'CIOH, as, for example, the sulfo-fatty acid of the formula The salts of the sulfo-fatty acids can be sodium, potassium, magnesium, or ammonium salts or salts produced from an amine or an organic base, preferably one having a maximum of 6 carbon atoms. The sulfo-fatty acids can be present as monoor di-salts, the di-salts being preferred. For the sake of simplicity, hereinafter the salts of sulfo-fatty acids will be called di-salts, though this term is intended to cover the monosalts as well.

Sulfonation products which contain sulfo-fatty acids or salts thereof in admixture with one another are suitable for use in the preparation of the pourable and free-flowing detergents, wetting agents, and emulsifiers in accordance wtih the invention. These sulfonation products can be obtained, for example, by sulfonating mixtures of fatty acids with a sulfonating agent, such as, for example, sulfuric acid, chloro-sulfonic acid and the like in the customary manner.

In the preparation of the sulfo-fatty acid saltsi.e., di-salt component, in accordance with the invention, the fatty acids are generally of natural origin, and, in the production of the sulfo-fatty acid salt, the starting fat material is selected on the basis that its fatty acid composition will come closest to that which is required for producing the desired properties in the final sulfo-fatty acid salt.

Examples of fatty acids which are suitable include such as stearic, palmitic, oleic, coconut fatty acids, palm oil, palm kernel oil, and other natural fatty acids having similar compositions. However, fats which are formed predominantly of higher fatty acids are also sutiable. An instance of such a fat is tallow. The fatty acids may also be of synthetic origin.

The pourable free-flowing preparations according to the invention constitute excellent detergent, wetting, and emulsifier agents and can be used alone or in admixture with other conventional additives used in these applications. The maximum amount of non-ionic washactive material which can be present depends to a great extent on the physical nature of the pure wash-active material under the usual conditions of storage, and generally should not be greater than 50 wt. percent and preferably not greater than 40 wt. percent. In general, the content of non-ionic surface-active material in the preparations of the invention ranges from 10 to 35, and preferably from 15 to 30 wt. percent. The balance can consist exclusively of di-salts. However, as noted heretofore, the additives conventionally used in detergents as, for instance, wetting agents and emulsifiers, may also be present.

A particularly advantageous application of the compositions in accordance with the invention is as wash-agents for use in the washing and bleaching treatment of textiles In this connection, additives which impart to the final preparation a pH value within the range of 6 to 12 have proved particularly suitable. The pH value is determined using as test sample a 1% solution of a detergent composition. The pH range extending from 6 to 12 includes the agents intended as fine wash-agents and which are required to be regulated so as to have a slightly acid to alkaline pH, i.e., approximately within the range of 6 to 8.5 and preferably within the range of 7 to 8, as well as the agents intended for use as boiling wash-agents and having a pH value approximately within the range of 9 to 12 and preferably of 9.5 to 11.5.

The compositions in accordance with the invention may be employed in conjunction with neutral or alkaline reacting salts, slightly acid reacting compounds as well as with the customary agents used to improve foaming, soil removal, and such additives as bleaching agents, corrosion protection agents, etc.

A neutral reacting salt which is most advantageously used is sodium sulfate, the same additionally acting to improve the effectiveness of the combination in accordance with the invention. It can be replaced, however, in whole or in part by non-surfactive, neutral reacting organic salts, such as, for instance, non-surface-active arylsulfonate, exemplified by such compounds as benzene, toluene, or naphthaline sulfonates.

The wash-alkalis which are suitable for use in connection with the invention include the alkali carbonates, alkali bicarbonates, water-soluble alkali silicates, alkali orthophosphates, etc.

The compositions in accordance with the invention may be used to particular advantage in conjunction with the anhydrous phosphates. The anhydrous phosphates employed may be any pyrophosphate, polyphosphate, or metaphosphate; the tripolyphosphates and tetrapolyphosphates having been found to possess particular practical significance. The pyroand polyphosphates are alkaline in reaction and are, therefore, able when used alone in boiling wash-agent compositions to impart to the same the necessary alkalinity; however, the metaphosphates produce a slightly acid reaction and are therefore advantageously utilized in the production of fine-wash agents serving to decrease the pH value of the resulting combination. Examples of other phosphates suitable for the same purpose include the acid orthophosphates, and the acid pyrophosphates. Weak inorganic or organic acids or acid salts of strong inorganic acids, such as, for example, boric acid, citric acid, oxalic acid, lactic acid, glycolic acid, tartaric acid, amidosnlfonic acid, and sodium bisulfate are instances of other materials suitable for use in regulating the pH value of the washing agent.

Still further, the preparations in accordance with the invention may be used in combination with the other conventional substances as are used in wash-agents. These substances include inorganic or organic-active oxygen carriers, as, for example, the percompounds, such as percarbonates, persulfates, perorthophosphates, perpyrophosphates, perpolyphosphates, and, in particular, alkali metal perborates. Products functioning to improve the soil removal property and foaming qualities of the compositions are additionally included in the preparation of wash-agents. Instances of substances serving to improve the soil removal capacity include water-soluble colloids, and preferably those of an organic nature, as for example, the water-soluble salts of polymeric carboxylic acids, sizes, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acid sul furic acid esters of cellulose or starch.

The salts which may be added to the compositions in accordance with the invention may be derived from inorganic or organic bases and preferably from the alkalis, for example, from sodium, potassium and ammonium alkalis or from the easily soluble organic amines. Such salts include alkylolamines, for example, mono-, di-, or triethanolamine. It is true that the salts of amines and especially the salts of alkylolamines often have poor properties of pulverulence, so that the amounts of these substances that can be used are limited.

The preparations in accordance with the invention can be manufactured in any desired manner by any process whereby the individual components of the final product can be mixed with one another. For example, the di-salt maybe added in dry form to the other compounds in paste form or a paste of water and the principal components of the final product can be prepared and the mixture then dried by any of a number of wellknown methods into the powdered final product under conditions whereby the free water is either largely removed by evaporation or becomes bound as water of crystallization, so that there is substantially no unbound water remaining in the final product. The drying may be effected by spray crystallization, spray drying, or processing in drum driers.

The non-ionic surface-active materials may, however, also be sprayed upon the initially pulverulent components of the mixture. This procedure is especially suited for calcined inorganic salts, such as carbonates, sulfates, phosphates, etc. In particular, anhydrous phosphates having a light bulk weight have proved suitable as supporting substances for non-ionic surfactants. Salts containing water of crystallization can also be calcined in the pres ence of the non-ionic surfactants, under conditions whereby the non-ionic surfactantsare picked up by the inorganic saltsduring the calcination process.

If these processes are performed in the presence of the di-salts, a more or less homogeneous mixture of all components is obtained, which can, by maintaining appropriate conditions, as for example during the conversion to powder of the aqueous paste containing all the principal components of the final product, be obtained as a substantially homogeneous product down to molecular dimensions.

It is also possible to mix the pulverulent components including the additional wash-active or other additives and non-ionic surfactants with the di-salts.

Care should be taken to ensure that the particle size of the di-salts is substantially smaller than that of the other pulverulent components or of the preparations containing thesame as then small amounts of di-salts will often sufiice to product a thin coating of di-salt on the surface of the particles of the other pulverulent components or on the surface of the preparations containing them and thus act to reduce or prevent mutual contact between particles containing sulfonates. In this connection, preferably the average particle size of the sulfo-fatty acid salts should amount to a maximum of /s and most preferably a maximum of that of the non-ionic surface active agents.

The minimum amount at which the di-salts exhibit their ameliatory effect depends somewhat on the nature and amount of any accompanying substances present. As most of the detergents, wetting agents and emulsifiers other than the non-ionics contain fairly large amounts of inorganic salts, an ameliatory effect can be recognized with a content of as little as 2 wt. percent of the total weight of the mixture. The di-salt content may also be larger, however, and may amount for example to at least 5%, in which case the di-salt content is to amount to at least 5% of the total weight of non-ionics and di-salt. The di-salt content may also be greater, however, and generally lies between 10 and 40 wt. percent of the mixture of non-ionics and di-salt. Large amounts, as for instance above 50 and 60 wt. percent, are generally used only in special cases.

In US. application Ser. No. 278,780, filed May 7, 1963, there are described pourable and free-flowing detergents, wetting agents, and emulsifiers, particularly in powdered form, having a content of surface-active sulfo-fatty acid ester salts and sulfo-fatty acid salts, and which can further contain non-ionic surfactants. In the case of the preparations described in application Ser. No. 278,780, the sulfo-fatty acid ester salts represent a critical component and are required to be present in an amount of at least 35 wt. percent with reference to the mixture of fatty acid ester salts and non-ionics. In the compositions of the present invention there are substantially no sulfofatty acid ester salts present. If they should be present, their quantity is less than 35% by weight with reference to the mixture of fatty acid ester salts and non-ionics.

The following examples illustrate the invention without limiting it thereto:

A number of compositions were prepared for evaluating their effectiveness as detergents, wetting agents, emulsifiers, namely powdery preparations containing a di-salt, and similar powdery preparations substantially free of disalts were prepared for evaluation under comparative conditions. In making the test powders, the component materials were dissolved and the resulting aqueous solutions converted in a spray dried to a fine powder having a moisture content of about 2 to 7%. All of the powders so prepared could be passed in their entirety through a sieve having a clear mesh width of 4.25 mm. 230 cc. of each of the powders were then filled into detergent boxes, sealed and stored in an atmospheric test chamber, through which air was circulated, for 7 days at 32 C. and relative humidity. The detergent boxes which were used were made of the usual strawboard and contained no lining or additive for preventing the exchange of moisture through the box walls. At the end of this period, the boxes were opened and their contents were examined for caking and tested for pourability.

In order to exclude the introduction of any possible error resulting from contact with the human hand, the apparatus (which is commercially available) shown in the drawing and described hereinafter was used in the experirnental procedures.

The apparatus consisted of a Plexiglas drum 1 having a cylindrical middle portion and open-ended conically tapering end portions. The total length of the Plexiglas drum amounted to 26.5 cm., the diameter of each end opening to 5 cm. and the diameter of the central, cylindrical portion to 16 cm. The central cylindrical portion measured 5 cm. in length. A shaft, the extension of which does not touch the drum axis, is arranged on the central cylindrical portion and is so attached thereto that with the laterally attached shaft in the horizontal position, the axis of the drum forms an angle of 79 degrees with the horizontal. The shaft attached to the central portion of the drum is connected in the horizontal position with the shaft of the speed-controlled electric motor 2. One of the two drum openings is then closed, the contents of a test box of detergent is poured through the other upwardly directed drum opening and a screen 3 having a clear mesh spacing of 4.25 mm. placed thereover. The motor is then started, the rotary speed always being adjusted to 40 revolutions per minute. The time is measured from the starting of the motor until all of the powder has passed through the screen or to the end of the time set for the experiment. The experiment is generally stopped where no appreciable amount of powder has flown through the screen. The residue remaining on the screen is collected and weighted.

The results as stated in the examples hereinafter, therefore, characterize on the one hand the. tendency of the powder to cake and on the other hand its ability to flow freely. The tendency of the powder to cake can be appreciated from the amount of residue left on the screen while the time it take for the powder to run through the sieve is a measure of its free-flowing ability.

The data obtained in the experiments are recorded in the following table: unless otherwise expressly stated, the salts are sodium salts and, in the case of the sulfonated fatty acid salts, they are disodium salts.

Wt percent left on screen Siove runthrough time, min.

Example Number Composition of the Preparation 30% product made by addition of 10 mols ethylene oxide with 1 mol of a fatty alcohol made by reduction of tallow fatty acid (Iodine N 0.:

50). 10% NaiPzoy. 60% Nazsoi.

30% product made by addition of 10 tools ethylene oxide with 1 mol of a fatty alcohol made by reducing tallow fatty acid (Iodine No.=

50). 10% wsulfo-fatty acid salt from hydrogenated coconut fatty acid. 10% NaiPaO 50% NaisO 20% product made by addition of 10 6 mols ethylene oxide with 1 mol of a fatty alcohol made by reducing tallow fatty acid (Iodine No.= 50).

10% a-sulfo-fatty acid salt from bydrogenated coconut fatty acid.

We claim:

1. A substantially solid particulate composition characterized by outstanding pouring and free-flowing properties which in combination with water constitutes a surfaceaotive composition wherein the pouring and free-flowing properties thereof are derived from a combination consisting essentially of a non-ionic surface-active agent and a member selected from the group consisting of alkali metal, alkaline earth metal and ammonium salts of alpha-sulfo fatty acids having about 10 to 24 carbon atoms in the fatty acid portion of its molecule said surface active agent being present in an amount of from to 50% by weight, the remainder being said wsulfo fatty acid salt.

2. A surface-active composition according to claim 1 wherein said salt of a sulfo-fatty acid has 12 to 18 carbon atoms in its molecule.

3. A surface-active composition according to claim 1 wherein said salt of a sulfo-fa-tty acid is a di-salt.

4. A surface-active composition according to claim 1 wherein said non-ionic surface-active agent is present in said composition in an amount of at most 50 wt. percent based on the total weight of said composition.

5. A surface-active composition according to claim 1 wherein said non-ionic surface-active agent is present in said composition in an amount of up to 40 wt. percent based on the total Weight of said composition.

6. A surface-active composition according to claim 1 wherein said non-ionic surface-active agent is present in said composition in an amount of from 5 to 35 Wt. percent based on the total weight of said composition.

7. A surface-active composition according to claim 1 wherein said sulfo-fatty acid salt is present in said composition in an amount of 70 Wt. percent based on the total Weight of said non-ionic agent and salt of a sulfo-fatty acid.

8. A surface-active composition according to claim 1 wherein said sulfo-fatty acid salt is present in said composition in an amount of wt. percent based on the total weight of said non-ionic agent and salt of a sulfofatty acid.

9. A surface-active composition according to claim 1 wherein said sulfo-fatty acid salt is present in said composition in an amount of 50 wt. percent based on the total weight of said non-ionic agent and salt of a sulfo-fatty acid.

10. A surface-active composition according to claim 1 wherein said non-ionic surface-active agent and said salt of a sulfa-fatty acid are each in discrete particle form. 11. A surface-active composition according to claim 1 wherein said non-ionic surface-active agent and said salt of a sulfo-fatty acid are present together in particle form, both being present in the same particle in hornOgenOus mixture.

12. A surface-active composition according to claim 14 wherein the average particle size of the particles containing the sulfa-fatty acid salt is at most that of the average particle size of those particles containing the nonionic surface-active agent.

13. A surface-active composition according to claim 10 wherein the average particle size of the particles contaning the sul-fo-fatty acid salt is at most that of the average particle size of those particles containing the nonionic surfaceactive agent.

14. A surface-active composition according to claim 10 wherein the surfaces of the particles containing the non-ionic surface-active agent are coated with di-salt.

15. A surface-active composition characterized by outstanding pouring and free-flowing properties comprising 20% of a product made by addition of 10 mols ethylene oxide to 1 mol of a fatty acid obtained by reducing tallow fatty acid having an iodine number of 50 10% a-sulfo-fatty acid salt obtained from hydrogenated coconut fatty acid N34P207 60% Na SO References Cited UNITED STATES PATENTS 2,195,145 3/1940 Crittenden 252-161 XR 2,195,186 3/1940 Moyer 252-161 XR 2,460,968 2/1949 Bert et al. 252161 XR 2,469,493 5/1949 Barker 25216l 2,555,285 5/1951 Black 252-161 2,742,436 4/1956 Jenkins 252161 2,867,586 1/1959 Weil et al. 252-152 XR 3,104,247 9/1963 Gavlin et al. 260400 3,159,581 12/1964 Diehl 252152 3,274,117 9/1966 Stein et al. 252-161 LEON D. ROSDOL, Primary Examiner.

ALBERT T. MEYERS, S. E. DARDEN, Examiners. 

1. A SUBSTANTIALLY SOLID PARTICULATE COMPOSITION CHARACTERIZED BY OUTSTANDING POURING AND FREE-FLOWING PROPERTIES WHICH IN COMBINATION WHEREIN THE POURING AND FREE-FLOWING PROPERTIES THEREOF ARE DERIVED FROM A COMBINATION CONSISTING ESSENTIALLY OF A NON-IONIC SURFACE-ACTIVE AGENT AND A MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL, ALKALINE EARTH METAL AND AMMONIUM SALTS OF ALPHA-SULFO FATTY ACIDS HAVING ABOUT 10 TO 24 CARBON ATOMS IN THE FATTY ACID PORTION OF ITS MOLECULE SAID SURFACE ACTIVE AGENT BEING PRESENT IN AN AMOUNT OF FROM 5 TO 50% BY WEIGHT, THE REMAINDER BEING SAID A-SULFO FATTY ACID SALT. 